OIL REFINERY

PLANT

CONVERSION
 CATALYTIC CRACKING
UNIT
Widely used in the crude oil refining
industry to convert viscous feedstocks
into more valuable naphtha and lighter
products

a central process in refining in which

heavy gas oil range feeds are subjected to
heat in the presence of a catalyst and
large molecules crack into smaller
molecules in the gasoline and
surrounding ranges
 Catalytic cracking
Example :
 THREE PARTS OF
CATALYTIC CRACKING
HARDWARE

• Reaction section (Reaction

Chamber)
• Regeneration (Regenerator)
• Fractionation (Fractionator)
PROCESS FLOW DIAGRAM OF
CATALYTIC CRACKING UNIT
 REACTION SECTION
The catalytic feed is pumped through the heater
and mixed with catalyst being pumped into a
reaction chamber

By the time the feed reaches the vessel, the

cracking process is well underway

2 types of catalyst used : beads and particles

The beads are 1⁄8 to 1⁄4 inch in diameter. The

particles are much smaller and look like baby
powder.
 REGENERATION
During the cracking process, the cracked
hydrocarbon is formed as a coke

The coke ends up as a deposit on the catalyst and

as the catalyst surface is covered up, the catalyst
becomes inactive (spent).

To remove the carbon, the spent catalyst is pumped

to a vessel called regenerator

Heated air at about 1100°F is mixed with the spent

catalyst and a chemical reaction takes place:
• 𝐶 + 𝑂2 → 𝐶𝑂 𝑎𝑛𝑑 𝐶𝑂2 (𝑜𝑙𝑑𝑒𝑟 𝑐𝑎𝑡𝑎𝑙𝑦𝑡𝑖𝑐 𝑐𝑟𝑎𝑐𝑘𝑒𝑟𝑠)
• 𝐶 + 𝑂2 → 𝐶𝑂2 (𝑛𝑒𝑤𝑒𝑟 𝑐𝑎𝑡𝑎𝑙𝑦𝑡𝑖𝑐 𝑐𝑟𝑎𝑐𝑘𝑒𝑟𝑠)
 REGENERATOR

The process is called oxidation

From the bottom of the regenerator, the freshly

regenerated catalyst is ready to be mixed with the
catalytic feed on its way to the reaction chamber
 FRACTIONATOR

When the cracked product leaves the reaction

chamber, it is charged or pumped in to a
fractionating column (fractionator). The products
separated generally are:
• Gases (C4 and lighter)
• Cat Gasoline
• Cat Light gas oil
• Cat Heavy gas oil
• Cycle Oil (from the bottom of fractionator)
 FACTORS AFFECTING CATALYTIC
CRACKER REACTION CHAMBER YIELDS
• THE QUALITY OF FEED - The important feed
qualities used are the hydrocarbon content. the
feed is said to be paraffinic because of its higher
conversion and gasoline yield

• REACTOR TEMPERATURE - the higher the

temperature, the more cracking will occur

• FEED RATE AND RECYCLE RATE - the higher

the feed rates, the more increasing volume will
occur at the bottom of fractionators.
 FACTORS AFFECTING CATALYTIC
CRACKER REACTION CHAMBER YIELDS
• TIME OF DAY AND TEMPERATURE –
in order to regenerate the spent catalyst, fresh air
is pumped into the regenerator continuously
As the temperature of the air outside goes down,
the air gets more dense
Since the blowers that pump the air operate at
fixed speed, more oxygen is actually pumped into
the regenerator when it’s cold than when it’s hot
The more oxygen, the more coke burned off the
catalyst. The fresher the catalyst, the better the
reaction. The better the reaction, the more
gasoline produced
 CATALYTIC REFORMING
UNIT
Catalytic reforming is a process used to convert
low-octane naphthas into high-octane gasoline
blending components called reformates

Converts :

Low octane linear hydrocarbons (paraffins) branched

alkanes (isoparaffins)

Paraffins napthenes

Napthenes high octane aromatic hydrocarbons

 CATALYTIC REFORMING
HARDWARE

• Reaction section
• Product recovery section
PROCESS FLOW DIAGRAM OF
CATALYTIC REFORMING UNIT
H2 RECYCLE H2 / C1
 REACTION SECTION

Most processes use platinum as the

active catalyst

Three reactors in series are used. The

reactors operate at 200–500 psi
pressure and 900–975°F. The vessels
are in spherical shape
 REACTION SECTION

The naphtha feed is pressurized, heated and

charged to the series of reactors containing catalyst

The effluent from the last reactor is cooled and sent

to a separator to remove the hydrogen-rich gas
stream from the top of the separator for recycling.
 REACTION SECTION
Hydrogen is an important by-product of catalytic
reforming

Hydrogen is used for reforming process in the

reactor

Hydrogen must be mixed with the feed to keep a

high concentration of hydrogen vapor in the
reactors to prevent carbon atoms from depositing
on the catalyst
 REACTION SECTION

the carbon reacts with the hydrogen and forms a

hydrocarbon gas. Part of the hydrogen stream is
recycled to the feed while the other part is sent to
the gas plant.
 REACTION SECTION

The liquid product from the bottom of the separator

is sent to a fractionator called a stabilizer (or
butanizer)

The butanizer makes a bottom product called

reformate; butanes and lighter go overhead and are
sent to the saturated gas plant
 REGENERATION

After an interval of operations, coke deposits on the

catalyst cause a decline in activity

Symptoms of the decline are : reduced octane

numbers, lower reformate yield per barrel of feed or
both

The plant must be shut down to regenerate the

catalyst but a continuous flow design was devised
by adding another reactor
 REGENERATION

At any one time, three of the reactors are in

operation, the fourth reactor being in the
regeneration mode

Regeneration is accomplished by admitting hot air

to remove the carbon from the catalyst, forming
carbon monoxide and carbon dioxide
 HYDROCRACKING UNIT
Hydrocracking is a two-stage process that
combines catalytic cracking and hydrogenation
The process employs high pressure, high
temperature, a catalyst, and hydrogen
The process is used for feedstocks that are difficult
to process by either catalytic cracking or reforming

The process gives a high yield of good quality

gasoline.

The process produces large amounts of isobutane

for alkylation feedstock
 HYDROCRACKING
HARDWARE
Catalyst - compounds of sulfur with cobalt
molybdenum (CoMo) or nickel plus
alumina

Feed is mixed with hydrogen vapor, heated to 550-

750 F, pressurized to 1200-2000 psi and charged
to the first stage reactor

Limited hydrocracking also occurs - about 40-50%

of the feed is cracked to gasoline
 HYDROCRACKING
HARDWARE

There are two main chemical reactions occurring in

the hydrocracker: catalytic cracking of heavy
hydrocarbons into lighter unsaturated hydrocarbons
and the saturation of these newly formed
hydrocarbons with hydrogen

The catalytic cracking of the heavier hydrocarbons

uses heat and causes the feed to be cooled as it
progresses through the reactor
 HYDROCRACKING
HARDWARE

The saturation of the lighter hydrocarbons releases

heat and causes the feed and products to heat up
as they proceed through the reactor

Hydrogen is also used to control the temperature of

the reactor—it is fed into the reactor at different
points. This keeps the reactor temperature from
cooling to the point that cracking will not occur and
from rising too high as to jeopardize the safety of
the operation.
 HYDROCRACKING
HARDWARE

After the hydrocarbon leaves the first stage, it is

cooled and liquefied and then sent through a
hydrogen separator. Hydrogen is recycled to the
feedstock. The liquid is charged to a fractionator.
Depending on the products desired (gasoline
components, jet fuel, and gas oil), the fractionator is
run to cut out some portion of the first-stage reactor
out-turn
 HYDROCRACKING
HARDWARE

Fractionator bottoms are mixed with a hydrogen

stream and charged to the second stage. Since this
material has already been subjected to
some hydrogenation, cracking, and reforming in the
first stage, the operations of the second stage are
more severe with higher temperatures and
pressures. As with the first stage, the second-stage
product is separated from the hydrogen and
charged to the fractionator.
PROCESS FLOW DIAGRAM OF
HYDROCRACKING UNIT
 ISOMERIZATION UNIT

The isomerization unit converts linear

molecules to higher-octane branched
molecules for blending into gasoline or feed
to alkylation units
• Butane isomerization
• Pentane / hexane isomerization
 BUTANE
ISOMERIZATION
The feed to butane isomerization unit is normal
butane or mixed butanes (iso and normal).
The butanes should not have any trace of olefins
which would deactivate the catalyst
The butanes are fed to a feed preparation column
where isobutane is removed; the high purity normal
butane is then mixed with a small amount of
hydrogen and chloride and charged to a reactor
containing a platinum catalyst

The catalyst causes the normal butane to reform

itself into its isomer, isobutane
 BUTANE
ISOMERIZATION
The stream coming from the reactor contains about
the followings:
60% isobutene
40% normal butane
A minor amount of propane and lighter

In a fractionator, the latter are split out and sent to

the fuel system. The butanes are recycled to the
feed fractionator so that the normal butane can be
rerun
PROCESS FLOW DIAGRAM OF
BUTANE ISOMERIZATION UNIT
 PENTANE / HEXANE
ISOMERIZATION
Pentane/hexane (C5/C6) isomerization processes
increase the octane of light gasoline
the C5 / C6 isomerization unit may have a feed
fractionator that concentrates the normal pentanes
and hexanes, rejecting the isomers
The normal paraffins are mixed with a small
amount of hydrogen and organic chlorides and
charged to a reactor
The catalyst will cause conversion of about 50% of
the feed to isomers (isomerate), so the reactor
product can be fractionated to recycle the normal
pentanes to extinction
 PENTANE / HEXANE
ISOMERIZATION

Since the hexanes boil at a higher temperature

than the normal pentane, but the isopentane boils
at a lower temperature, the cost of the additional
hexane splitter sometimes precludes recycling the
normal hexane
PROCESS FLOW DIAGRAM OF PENTANE /
HEXANE ISOMERIZATION UNIT
 USES OF BUTANE AND
PENTANE / HEXANE
ISOMERIZATION

Butane (C4) isomerization is used to satisfy the feed

needs of alkylation by converting normal butane to
isobutane

Pentane / hexane (C5 / C6) isomerization increase

the octane number of light gasoline components
 ALKYLATION UNIT

used to convert isobutane and low-molecular-

weight alkenes (primarily a mixture of propylene
and butylene) into alkylate, a high octane gasoline
component

This involves reacting isobutane with some type of

light olefin, typically either propylene or butylene
 ALKYLATION HARDWARE

Chiller

• Alkylation with sulfuric acid catalyst works at

temperatures of about 40°F.
• The olefin feed is mixed with a stream of
isobutane and a stream of sulfuric acid and
pumped through a chiller.
• The olefin consists of propylene and butylene.
 ALKYLATION HARDWARE
Reactor

• The reaction time for alkylation process is

relatively slow, from 15 to 20 minutes, so the
mixture is pumped into a battery of large
reactors.
• As the liquid passes through the reactors, it
encounters mixers to assure that the olefins
come in good contact with the isobutane in the
presence of the acid, permitting the reaction to
occur
 ALKYLATION HARDWARE
Acid separator

• The function of acid separator is to separate

hydrocarbon and acid.
• The mixture moves to a vessel where no mixing
takes place, and the acid and hydrocarbons
separate like oil and water.
• The hydrocarbon is drawn off the top while the
acid is drawn of the bottom.
• The acid is then recycled back to the feed side
• The acid separator is also referred to as the acid
settler.
 ALKYLATION HARDWARE

Caustic wash

• The hydrocarbon from the acid separator will

have some traces of acid in it, so it is treated with
caustic soda in a vessel.
• Caustic soda neutralized the acid in hydrocarbon
 ALKYLATION HARDWARE

Debutanizer

• The primary product from an alkylation unit is

C5+ alkylate
• Normal propane, butane and isobutane from top
of debutanizer is send to deisobutanizer
 ALKYLATION HARDWARE

Deisobutanizer

• Deisobutanizer separate butane from isobutane

and propane
• Normal propane and isobutane from top of
deisobutanizer is send to depropanizer
 ALKYLATION HARDWARE

Depropanizer

• Depropanizer separate isobutane from propane

PROCESS FLOW DIAGRAM OF ALKYLATION
UNIT
OIL REFINERY
PLANT

TREATMENT
 HYDROTREATING UNIT

to remove sulfur and other contaminants from

intermediate streams before blending into a
finished refined product or before being fed into
another refinery process unit.

Also known as: hydrodesulfurization

Refinery streams that have C6 and heavier

hydrocarbons in them are likely to have some sulfur
compounds
 HYDROTREATING
HARDWARE

In the hydrotreating process, the stream is mixed

with hydrogen and heated to 500-800 F.

The oil combined with the hydrogen is then charged

to a vessel filled with a catalyst in pellet form
 HYDROTREATING
HARDWARE
In the presence of the catalyst, several reactions
take place:
i. The hydrogen combines with the sulfur atoms to
form hydrogen sulfide (H2S).
ii. Some nitrogen compounds are converted to
ammonia.
iii. Any metals entrained in the oil are deposited on
the catalyst.
iv. Some of the olefins, aromatics or naphthenes
get hydrogen saturated and some cracking takes
place, causing the creation of some methane,
ethane, propane and butanes
 HYDROTREATING
HARDWARE

The reaction products leave the reactor and after

cooling to a low temperature enter a liquid/gas
separator

The hydrogen-rich gas from the high-pressure

separation is recycled to combine with the
feedstock, and the low-pressure gas stream rich in
H2S is sent to a gas-treating unit where H2S is
removed
The clean gas is then suitable as fuel for the
refinery furnaces
 HYDROTREATING
HARDWARE

The liquid stream is the product from hydrotreating

and is normally sent to a stripping column for
removal of H2S and other undesirable components
Hydrodesulfurized products are blended or used as
catalytic reforming feedstock
PROCESS FLOW DIAGRAM OF
HYDROTREATING UNIT